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Cover image for Vol. 9 Issue 22

November 25, 2013

Volume 9, Issue 22

Pages 3725–3901

  1. Cover Picture

    1. Top of page
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    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Corrigendum
    8. Frontispiece
    9. Communications
    10. Frontispiece
    11. Full Papers
    12. Communication
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      Plasmonics: Resistless Nanoimprinting in Metal for Plasmonic Nanostructures (Small 22/2013) (page 3725)

      Leo T. Varghese, Li Fan, Yi Xuan, Chookiat Tansarawiput, Sangsik Kim and Minghao Qi

      Version of Record online: 18 NOV 2013 | DOI: 10.1002/smll.201370134

      Thumbnail image of graphical abstract

      A simple metal nanopatterning process named resistless nanoimprinting in metal (RNIM) is proposed and demonstrated by Y. Xuan, M. Qi, and co-workers on page 3778. This allows metal films to be directly imprinted at low temperatures and low pressures without the need for resists or any intermediate layers. High-resolution patterns with smooth and vertical side-walls are generated on metals such as Ag and Au. The RNIM process can be used to pattern metals for applications in plasmonics, metamaterials, biological sensing, and microfluidics. A vivid image of a butterfly seen through a perforated metal film is illustrated in the cover image as a demonstration of extraordinary optical transmission.

  2. Inside Front Cover

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    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Corrigendum
    8. Frontispiece
    9. Communications
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    11. Full Papers
    12. Communication
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      Laser Spectroscopy: Watching Single Nanoparticles Grow in Real Time through Supercontinuum Spectroscopy (Small 22/2013) (page 3726)

      Lars O. Herrmann and Jeremy J. Baumberg

      Version of Record online: 18 NOV 2013 | DOI: 10.1002/smll.201370135

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      The growth of a single gold nanorod attached to a coverslip is observed in real time through supercontinuum dark field spectroscopy. The scattered light is collected with a high magnification lens. As reported on page 3743 by L. O. Herrmann and J. J. Baumberg, the frequency shift of the localized surface plasmons in the rod due to deposition of gold ions at the nanorod caps reveals quantitative information about its growth kinetics.

  3. Back Cover

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    4. Back Cover
    5. Masthead
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    9. Communications
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      Doped Nanocrystals: Tuning the Emission Colors of Semiconductor Nanocrystals Beyond their Bandgap Tunability: All in the Dope (Small 22/2013) (page 3904)

      Santanu Jana, Goutam Manna, Bhupendra B. Srivastava and Narayan Pradhan

      Version of Record online: 18 NOV 2013 | DOI: 10.1002/smll.201370136

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      Transition metal ion doped semiconductor nanocrystals emitting in the entire visible light spectrum are reported by N. Pradhan and co-workers on page 3753. The doping of Ag, Cr, Ni, and Cu ions is performed with a fixed size/composition of the CdxZn1−xS alloy host semiconductor nanocrystals and blue, green, yellow, and red (BGYR) emission colors are obtained, respectively. By designing different dual-doped nanocrystals, the dopant state positions are correlated.

  4. Masthead

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      Masthead: (Small 22/2013)

      Version of Record online: 18 NOV 2013 | DOI: 10.1002/smll.201370137

  5. Contents

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    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Corrigendum
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    9. Communications
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      Contents: (Small 22/2013) (pages 3727–3733)

      Version of Record online: 18 NOV 2013 | DOI: 10.1002/smll.201370138

  6. Corrigendum

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      Corrigendum: Plasmonic Amplifiers: Engineering Giant Light Enhancements by Tuning Resonances in Multiscale Plasmonic Nanostructures (page 3734)

      A. Chen, R. L. Miller, A. E. DePrince III, A. Joshi-Imre, E. Shevchenko, L. E. Ocola, S. K. Gray, U. Welp and V. K. Vlasko-Vlasov

      Version of Record online: 18 NOV 2013 | DOI: 10.1002/smll.201302442

      This article corrects:
  7. Frontispiece

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      Drug Delivery: Receptor-Specific Delivery of Protein Antigen to Dendritic Cells by a Nanoemulsion Formed Using Top-Down Non-Covalent Click Self-Assembly (Small 22/2013) (page 3735)

      B. J. Zeng, Y. P. Chuan, B. O'Sullivan, I. Caminschi, M. H. Lahoud, R. Thomas and A. P. J. Middelberg

      Version of Record online: 18 NOV 2013 | DOI: 10.1002/smll.201370139

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      A new approach to the bottomup self-assembly of drug delivery nanoemulsions is presented on page 3736 by A. P. J. Middelberg and co-workers. The method is based on the interfacial mixing of biosurfactant protein and closely-related biosurfactant peptide. Functional elements such as immune-evading PEG or a targeting antibody can be conjugated to DAMP4 using known approaches. Simple topdown sequential addition of conjugated DAMP4 to a nanoemulsion stabilized by peptide surfactant AM1 leads to selfassembly of the functional element at the emulsion interface. The resulting nanoemulsion can package protein antigen and deliver it in a targeted fashion to a receptor-selected subpopulation of cells.

  8. Communications

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    7. Corrigendum
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    9. Communications
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    12. Communication
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    1. Receptor-Specific Delivery of Protein Antigen to Dendritic Cells by a Nanoemulsion Formed Using Top-Down Non-Covalent Click Self-Assembly (pages 3736–3742)

      B. J. Zeng, Y. P. Chuan, B. O'Sullivan, I. Caminschi, M. H. Lahoud, R. Thomas and A. P. J. Middelberg

      Version of Record online: 18 APR 2013 | DOI: 10.1002/smll.201300078

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      A new class of targeted and immune-evading nanocarrier made using only biological components and facile processes is assembled in a bottom-up fashion. Simple top-down sequential addition of immune-evading or receptor-specific antibody elements conjugated to biosurfactant protein DAMP4 promotes self-assembly at an interface previously formed in the presence of peptide surfactant AM1, leading to a functional display at the interface through non-covalent molecular self-assembly.

    2. Watching Single Nanoparticles Grow in Real Time through Supercontinuum Spectroscopy (pages 3743–3747)

      Lars O. Herrmann and Jeremy J. Baumberg

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/smll.201300958

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      A fast dark-field scattering technique capturing full broadband spectra with millisecond time-resolution enables us to monitor the growth or assembly of single nano-objects in situ and in real time. Applying this technique to study the growth of single gold nanorods, together with scanning electron microscopy and finite-difference time-domain simulations, reveals precise quantitative information about gold nanorod growth kinetics.

    3. Fluorescent DNA Hydrogels Composed of Nucleic Acid-Stabilized Silver Nanoclusters (pages 3748–3752)

      Weiwei Guo, Ron Orbach, Iris Mironi-Harpaz, Dror Seliktar and Itamar Willner

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/smll.201300055

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      Y-shaped DNA units functionalized with Ag-nanoclusters are crosslinked by nucleic acids to yield fluorescent hydrogels with controlled luminescence properties.

    4. Tuning the Emission Colors of Semiconductor Nanocrystals Beyond their Bandgap Tunability: All in the Dope (pages 3753–3758)

      Santanu Jana, Goutam Manna, Bhupendra B. Srivastava and Narayan Pradhan

      Version of Record online: 24 JUN 2013 | DOI: 10.1002/smll.201300635

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      Adopting the concept of one dopant for one color, all the prominent emitting colors in the visible windows are obtained by doping selective dopants (Ag, Cu, Ni, and Cu) in an appropriate host (alloy of CdxZn1-xS) with fixed size/composition and bandgap. Analyzing the origin of these emissions the relative position of respective dopant states are correlated.

    5. Forced Assembly of Water-Dispersible Carbon Nanotubes Trapped in Paper for Cheap Gas Sensors (pages 3759–3764)

      Jian Wang, Xinyue Zhang, Xiaopeng Huang, Shujun Wang, Qiuping Qian, Wenbin Du and Yapei Wang

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/smll.201300655

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      A versatile and readily scalable approach to fabricate a cheap and sensitive paper gas sensor is described. Chemically acidified single-walled carbon nanotubes are assembled in paper, forming continuous sensing arrays with a low detection limit and high detection selectivity for ammonia gas.

    6. Colloidal Synthesis of Ternary AgFeS2 Nanocrystals and Their Transformation to Ag2S-Fe7S8 Heterodimers (pages 3765–3769)

      Shi-Kui Han, Chao Gu, Ming Gong, Ze-Ming Wang and Shu-Hong Yu

      Version of Record online: 5 MAY 2013 | DOI: 10.1002/smll.201300268

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      Ternary-/hetero-nanocrystals: a facile one-pot colloidal route for controlled synthesis of ternary AgFeS2 nanocrystals, which have a band gap of 1.21 eV, is presented for the first time. Such ternary AgFeS2 nanocrystals can transform to Ag2S-Fe7S8 heterodimers by internal thermal reaction at elevated temperature, providing a new route to synthesize semiconductor hetero-nanostructures.

  9. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Corrigendum
    8. Frontispiece
    9. Communications
    10. Frontispiece
    11. Full Papers
    12. Communication
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      Cell Fusion: Optically Induced Cell Fusion Using Bispecific Nanoparticles (Small 22/2013) (page 3770)

      Daniella Yeheskely-Hayon, Limor Minai, Lior Golan, Eldad J. Dann and Dvir Yelin

      Version of Record online: 18 NOV 2013 | DOI: 10.1002/smll.201370140

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      The image shows a high magnification scanning electron microscopy image of a dendritic (false color blue) and malignant B (false color green) cell pair coupled by bispecific gold nanoparticles. As described on page 3771 by D. Yeheskely-Hayon and co-workers, the cell pairs are irradiated by a sequence of femtosecond laser pulses, resulting in a wide-spread fusion and subsequent formation of dendritic-B cell hybrids, which could be used for stimulating the immune system to eliminate tumor cells. This novel approach for selective induction of cell fusion using bispecific nanoparticles and laser pulses could be useful for a variety of applications that call for selective fusion between cells within a large heterogenic cell population.

  10. Full Papers

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    3. Inside Front Cover
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    5. Masthead
    6. Contents
    7. Corrigendum
    8. Frontispiece
    9. Communications
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    11. Full Papers
    12. Communication
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    1. Optically Induced Cell Fusion Using Bispecific Nanoparticles (pages 3771–3777)

      Daniella Yeheskely-Hayon, Limor Minai, Lior Golan, Eldad J. Dann and Dvir Yelin

      Version of Record online: 21 JUN 2013 | DOI: 10.1002/smll.201300696

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      Selective attachment of malignant cells to antigen-presenting cells using bispecific nanoparticles is presented. Scanning electron microscopy shows a typical dendritic (false color blue) and Burkitt lymphoma B (false color green) cell pair coupled by gold nanoparticles (false color yellow). Irradiation of cell pairs by femtosecond laser pulses results in widespread fusion and the formation of dendritic–B cell hybrids.

    2. Resistless Nanoimprinting in Metal for Plasmonic Nanostructures (pages 3778–3783)

      Leo T. Varghese, Li Fan, Yi Xuan, Chookiat Tansarawiput, Sangsik Kim and Minghao Qi

      Version of Record online: 18 APR 2013 | DOI: 10.1002/smll.201300168

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      Direct imprinting of metal films by silicon molds without the need of resists or any intermediate layers is demonstrated using pressures of <4 MPa and temperatures of 25–150 °C. Three-dimensional metal structures with smooth and vertical sidewalls, down to sub-10 nm resolution, are generated in silver and gold films. Large-scale vivid images through extraordinary optical transmission and strong surface-enhanced Raman scattering substrates are realized quickly, repeatedly, and at a low-cost.

    3. Organic Field-Effect Transistor Memory Devices Using Discrete Ferritin Nanoparticle-Based Gate Dielectrics (pages 3784–3791)

      Beom Joon Kim, Yongmin Ko, Jeong Ho Cho and Jinhan Cho

      Version of Record online: 10 MAY 2013 | DOI: 10.1002/smll.201300522

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      A novel type of transistor memory device is prepared using protein multilayers. These devices display reversible shifts in the threshold voltage as a function of charge trapping and detrapping in the protein gate dielectric layers. This approach is extended to the preparation of flexible transistor memory devices that require low operating voltages and have reliable electrical and mechanical stability.

    4. Graphene/Polyaniline/Poly(4-styrenesulfonate) Hybrid Film with Uniform Surface Resistance and Its Flexible Dipole Tag Antenna Application (pages 3792–3798)

      Keun-Young Shin, Sunghun Cho and Jyongsik Jang

      Version of Record online: 5 MAY 2013 | DOI: 10.1002/smll.201203204

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      A graphene/polyaniline/poly(4-styrenesulfonate) (G/PANI/PSS)-based conducting paste is synthesized by mechanically mixing multilayer graphene with an aqueous solution of PANI/PSS. High concentrations of PSS are obtained, which increases the compatibility between the graphene matrix and the PANI nanofiller. This allows uniform surface resistance and good adhesion of the film to a flexible substrate. Patterned, screen-printed hybrid films are evaluated as dipole tag antennas.

    5. Multiwall Carbon Nanotubes Mediate Macrophage Activation and Promote Pulmonary Fibrosis Through TGF-β/Smad Signaling Pathway (pages 3799–3811)

      Peng Wang, Xin Nie, Yue Wang, Yang Li, Cuicui Ge, Lili Zhang, Liming Wang, Ru Bai, Zhiyun Chen, Yuliang Zhao and Chunying Chen

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/smll.201300607

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      Multiwall carbon nanotubes stimulate secretion of TGF-β1 in the lung by activation of alveolar macrophages, and subsequntly trigger the TGF-β/Smad signaling pathway in fibroblasts, which can upregulate the mRNA transcription of both ECM protease inhibitors and collagen type I/III.

    6. A Detailed Experimental and Theoretical Study into the Properties of C60 Dumbbell Junctions (pages 3812–3822)

      Katalin Gillemot, Charalambos Evangeli, Edmund Leary, Andrea La Rosa, M. Teresa González, Salvatore Filippone, Iain Grace, Gabino Rubio-Bollinger, Jaime Ferrer, Nazario Martín, Colin J. Lambert and Nicolás Agraït

      Version of Record online: 30 APR 2013 | DOI: 10.1002/smll.201300310

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      The conductance versus distance behavior of a single C60 dumbbell molecule trapped between two gold electrodes is reported. The presence of only one molecule in the junction is unambiguously identified by prior imaging. The current flows directly into the centre of the molecule, whilst random conductance fluctuations are kept low thanks to the low mobility of the molecule.

    7. Covalent Functionalization of Dipole-Modulating Molecules on Trilayer Graphene: An Avenue for Graphene-Interfaced Molecular Machines (pages 3823–3828)

      Phong Nguyen, Junwen Li, T. S. Sreeprasad, Kabeer Jasuja, Nihar Mohanty, Myles Ikenberry, Keith Hohn, Vivek B. Shenoy and Vikas Berry

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/smll.201300857

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      The effect of the change in the dipole moment of a tethered molecule on the carrier properties of functionalized trilayer graphene is demonstrated. Due to large carrier confinement and quantum capacitance (72.5 μF cm−2), the isomerisation of azobenzene molecules (dipole moment change of 3D or 0.097 V) leads to the generation of a large effective gating voltage (34 V) and an increase in hole density by 440 000 holes μm−2.

    8. Direct Growth of Polyaniline Chains from N-Doped Sites of Carbon Nanotubes (pages 3829–3833)

      Atta Ul Haq, Joonwon Lim, Je Moon Yun, Won Jun Lee, Tae Hee Han and Sang Ouk Kim

      Version of Record online: 2 MAY 2013 | DOI: 10.1002/smll.201300625

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      An efficient route to hybrid systems of conducting polymers directly grafted from graphitic dopant sites is introduced. Nitrogen (N)-doped sites on carbon nanotubes (CNTs) initiate the polymerization of aniline, which generates hybrids consisting of polyaniline directly grafted onto the CNT walls. The resultant materials exhibit excellent electrochemical performance for charge collectors of supercapacitors.

    9. Cell Surface Receptor Targeted Biomimetic Apatite Nanocrystals for Cancer Therapy (pages 3834–3844)

      Michele Iafisco, Josè Manuel Delgado-Lopez, Elena Maria Varoni, Anna Tampieri, Lia Rimondini, Jaime Gomez-Morales and Maria Prat

      Version of Record online: 18 APR 2013 | DOI: 10.1002/smll.201202843

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      Apatite nanoparticles functionalized with the chemotherapeutic doxorubicin and a monoclonal antibody targeting tumor cells overexpressing the tumor associated marker Met/Hepatocyte Growth Factor receptor specifically bind to and are internalized in cells expressing the receptor, and discharge doxorubicin, which reaches the nucleus and exert cytotoxicity. This work opens new perspectives in the use of nanocrystalline apatites as new platform for theranostic applications in nanomedicine.

  11. Communication

    1. Top of page
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    6. Contents
    7. Corrigendum
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    12. Communication
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    1. An E3-14.7K Peptide that Promotes Microtubules-Mediated Transport of Plasmid DNA Increases Polyplexes Transfection Efficiency (pages 3845–3851)

      Lucie Pigeon, Cristine Gonçalves, David Gosset, Chantal Pichon and Patrick Midoux

      Version of Record online: 10 MAY 2013 | DOI: 10.1002/smll.201300217

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      P79-98 peptide responsible for the E3-14.7K/FIP-1 interaction with microtubules is linked to a plasmid DNA to favor its cytosolic migration during cell transfection with a cationic polymer. P79-98 allows docking and transport of DNA along microtubules. P79-98/peGFP polyplexes enhance drastically the number of transfected cells. This is a real breakthrough in the non-viral gene delivery field.

  12. Full Papers

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    1. Switchable Transport Strategy to Deposit Active Fe/Fe3C Cores into Hollow Microporous Carbons for Efficient Chromium Removal (pages 3852–3857)

      Dong-Hai Liu, Yue Guo, Lu-Hua Zhang, Wen-Cui Li, Tao Sun and An-Hui Lu

      Version of Record online: 10 JUN 2013 | DOI: 10.1002/smll.201300276

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      Hollow structures with microporous carbon shells and Fe/Fe3C active cores are fabricated through a switchable transport strategy, and show excellent CrVI removal efficiency and high magnetization. The micropore shells can effectively capture CrVI from the surroundings and protect the internal Fe/Fe3C that attracts/reacts with CrVI.

    2. Enhanced Light Out-Coupling of OLEDs with Low Haze by Inserting Randomly Dispersed Nanopillar Arrays Formed by Lateral Phase Separation of Polymer Blends (pages 3858–3863)

      Cholho Lee and Jang-Joo Kim

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/smll.201300068

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      Phosphorescent OLEDs with randomly dispersed nanopillar arrays fabricated by phase separation of polymer blends as light-extracting layers show 24% external quantum efficiency enhancement with Lambertian emission patterns, spectrum-independent viewing angles, and only a small increment in haze. This method is an easily controllable, low cost process applicable to large-area fabrication.

    3. Enhanced Photocatalytic Performances of CeO2/TiO2 Nanobelt Heterostructures (pages 3864–3872)

      Jian Tian, Yuanhua Sang, Zhenhuan Zhao, Weijia Zhou, Dongzhou Wang, Xueliang Kang, Hong Liu, Jiyang Wang, Shaowei Chen, Huaqiang Cai and Hui Huang

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/smll.201202346

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      The enhanced photocatalytic performance of CeO2/TiO2 heterostructured nanobelts is attributed to a novel capture–photodegradation–release degradation mechanism. During the photocatalytic process, MO molecules are captured by CeO2 nanoparticles on the surface of the heterostructure, then quickly photodegraded under UV or visible light irradiation, and ultimately the degradation products are released to external environment.

    4. Cu Nanoclusters with Aggregation Induced Emission Enhancement (pages 3873–3879)

      Xiaofang Jia, Jing Li and Erkang Wang

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/smll.201300896

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      Fluorescent Cu nanoclusters (NCs) are selectively synthesized via the surface etching route from the nonluminescent nanocrystals. Intriguingly, the as-prepared CuNCs exhibit an aggregation-induced emission enhancement effect. The CuNCs emit a faint light when dispersed in aqueous solution, but generate a striking fluorescence intensity enhancement upon aggregation.

    5. Enhanced Intercalation Dynamics and Stability of Engineered Micro/Nano-Structured Electrode Materials: Vanadium Oxide Mesocrystals (pages 3880–3886)

      Evan Uchaker, Meng Gu, Nan Zhou, Yanwei Li, Chongmin Wang and Guozhong Cao

      Version of Record online: 5 MAY 2013 | DOI: 10.1002/smll.201203187

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      An additive and template free process is developed for the facile synthesis of VO2(B) mesocrystals. Microscopy results demonstrate that the six-armed star architectures are composed of stacked nanosheets oriented along the [100] crystallographic register. The synthesized VO2(B) mesocrystals are tested as a cathode material for lithium-ion batteries and show excellent capacity values at high discharge rates that are superior to non-oriented nanoparticle counterparts.

    6. Surface-Layer Lattices as Patterning Element for Multimeric Extremozymes (pages 3887–3894)

      Judith Ferner-Ortner-Bleckmann, Nicola Gelbmann, Manfred Tesarz, Eva M. Egelseer and Uwe B. Sleytr

      Version of Record online: 12 JUN 2013 | DOI: 10.1002/smll.201201014

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      Novel self-assembling biocatalysts based on a bacterial surface-layer (S-layer) protein and multimeric extremozymes are successfully produced. A tetrameric or a trimeric enzyme is genetically fused to an S-layer protein through a flexible peptide linker. By recrystallization of the S-layer/extremozyme fusion proteins on solid supports, active enzyme multimers are exposed in an accurate spatial distribution on the surface of the square S-layer lattice.

    7. Magneto-Controllable Capture and Release of Cancer Cells by Using a Micropillar Device Decorated with Graphite Oxide-Coated Magnetic Nanoparticles (pages 3895–3901)

      Xiaolei Yu, Rongxiang He, Shasha Li, Bo Cai, Libo Zhao, Lei Liao, Wei Liu, Qian Zeng, Hao Wang, Shi-Shang Guo and Xing-Zhong Zhao

      Version of Record online: 5 MAY 2013 | DOI: 10.1002/smll.201300169

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      A micropillar device decorated with graphite oxide-coated magnetic nanoparticles is fabricated for magneto-controllable capture and release of cancer cells. Notably, the captured cancer cells are able to be released from the micropillars with high viability upon the removal of external magnetic field, which potentially facilitates subsequent analysis.

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